TY - JOUR
T1 - Chiral Phosphite-Thioether Complexes of Palladium(0). Comments on the Pd, Rh, and Ir Regio-and-Enantioselective Allylic Alkylations of PhCH=CHCH(OAc)R, R = H, Me, Et
AU - Selvakumar, Kumaravel
AU - Valentini, Massimiliano
AU - Pregosin, Paul S.
AU - Albinati, Alberto
PY - 1999/10/25
Y1 - 1999/10/25
N2 - The new chiral auxiliary (R)-2-ethylthio-1-(phenylethyl)-(R)-binaphthyl phosphite, 1, and three stable Pd(0) olefin complexes containing this chelate, 2-4, have been synthesized. The structure of the maleic anhydride complex 3 has been determined by X-ray diffraction methods. Solution details for 2-4 and aspects of their dynamics have been elucidated via 2-D NMR spectroscopy. The fumaronitrile complex 2 exchanges intramolecularly, whereas the maleic anhydride and pentenedione derivatives, 3 and 4, respectively, exchange intermolecularly. Ligand 1 has been used as auxiliary in the Pd, Rh, and Ir regio- and enantioselective allylic alkylation reactions of PhCH=CHCH(OAc)R, R = H, Me, Et, with the anion of dimethyl malonate. Modest to good selectivities are reported.
AB - The new chiral auxiliary (R)-2-ethylthio-1-(phenylethyl)-(R)-binaphthyl phosphite, 1, and three stable Pd(0) olefin complexes containing this chelate, 2-4, have been synthesized. The structure of the maleic anhydride complex 3 has been determined by X-ray diffraction methods. Solution details for 2-4 and aspects of their dynamics have been elucidated via 2-D NMR spectroscopy. The fumaronitrile complex 2 exchanges intramolecularly, whereas the maleic anhydride and pentenedione derivatives, 3 and 4, respectively, exchange intermolecularly. Ligand 1 has been used as auxiliary in the Pd, Rh, and Ir regio- and enantioselective allylic alkylation reactions of PhCH=CHCH(OAc)R, R = H, Me, Et, with the anion of dimethyl malonate. Modest to good selectivities are reported.
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U2 - 10.1021/om990452o
DO - 10.1021/om990452o
M3 - Article
AN - SCOPUS:0001742308
SN - 0276-7333
VL - 18
SP - 4591
EP - 4597
JO - Organometallics
JF - Organometallics
IS - 22
ER -